2-alkyl substituted-4-methyl-1,3-dioxanes



United States Patent 3,423,430 Z-ALKYL SUBSTITUTED-4-METHYL-1,3-DlOXANES Arno Cahn, Pearl River, N.Y., and Allan H. Gilbert, West Englewood, N.I., assignors to Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. Original application Sept. 4, 1962, Ser. No. 221,318, now Patent No. 3,326,746, dated June 20, 1967. Divided and this application Sept. 13, 1966, Ser. No. 623,476 US. Cl. 260-3407 1 Claim Int. Cl. C07d 15/04 This is a divisional application of Ser. No. 221,318, filed Sept. 4, 1962, now US. Patent 3,326,746.

This invention relates to a perfume. More particularly, it relates to a cleaning product with this perfume therein.

It is known that natural geranium oil may be used as a perfume. However, the natural oil is a complicated mixture of numerous components and it has not beeh possible, heretofore, to form a synthetic product with a suitable geranium note. Even blends prepared by combining the known components of the natural oil do not have the proper odor characteristics.

It is also known to incorporate a perfume into a cleaning product, e.g., a dishwasher product. If, however, the cleaning product contains a chlorine-releasing agent, the prior art perfumes are not satisfactory since they do not overcome the pungent odor resulting from the use of this product. For example, an unsaturated perfume may lose its odoriferous properties and stability because the unsaturation is attacked by the chlorine-releasing agent.

It has now been discovered that a synthetic perfume may be prepared which has a satisfactory geranium-rose note, Furthermore, this perfume may be advantageously employed in cleaning products including those products having chlorine-releasing agents therein. Such a perfume has the following generic structure:

wherein R is an alkyl group having 4 to 9 carbon atoms; R is selected from the group consisting of hydrogen and a C, to C, alkyl group; and R is selected from the group consisting of hydrogen and methyl.

It is important for the success of the present invention to have a 1,3-dioxane with alkvl groups in at least the 2,4 positions. If R were the only alkyl group, such as isobutyl or l-ethylpropyl, the compounds therefrom would be devoid of any geranium-rose note. The number of carbon atoms in R is also important; there must be at least 4 carbon atoms but not more than 9 carbon atoms in a straight or branched chain. For example, if R, were isopropyl or decyl, the resulting compound would not possess the required geranium-rose note.

Another important feature lies in the 4-methyl su-bstituent in the above structure. The desired perfume would not be provided if higher alkyls, such as ethyl and isopropyl, were employed. Each of the ring carbons must have at least one hydrogen thereon. If a gem-dialkyl group is located on any of the ring carbons, the compounds therefrom do not have a geranium-rose note.

The 2,4-dialkyl-1,3-dioxanes of the present invention may be prepared in accordance with similar procedures known in the art for forming other 1,3-dioxanes. Generally about 1 to 1.5 equivalents of a 1,3-diol are reacted with about 1 equivalent of an aldehyde in the presence of, firstly, a solvent which azeotropes with water, e.g.,

3,423,430 Patented Jan. 21, 1969 "ice chloroform, ethylene dichloride and benzene, and, secondly, about 0.01% to about 10% of an acid catalyst, e.g., sulfuric acid, hydrochloric acid, p-toluenesulfonic acid and an insoluble resin acid of the sulfonic acid type. The temperature of the reaction is not critical but it is generally maintained between about 40 and 150 C., preferably between about 60 and 100 C.; time varies inversely from about 1 to 6 hours. Water is removed until the reaction is complete with subsequent cooling; neutralization with aqueous alkali, dry alkali, sodium carbonate or the like; washing; and distillation to provide the desired dioxane.

With respect to a second embodiment of this invention, the 2,4-dialkyl-l,3-dioxanes having the geranium-rose note may be incorporated into a cleaning product, e.g., a dishwasher formulation, to overcome the strong odor resulting from the chlorine-releasing compounds therein. The other ingredients usually included in the instant cleaning products besides the dioxanes and chlorinereleasing agents are soaps or non-soap detergents and phosphates. A cleaning product is broadly defined herein as a substance or a composition which removes undesirable dirt, food particles, stains or the like or which renders an item unsoiled. This, therefore, includes dishwashing compounds, dry bleaches, scouring cleansers, light-duty detergents, heavy-duty detergents, pelleted detergents, soap products and scouring pads.

The perfume content depends upon the specific dioxane and the type of cleaning product. Generally, the dioxane perfume is employed in an amount up to about 0.5 part, preferably between about .05 to .25 part, per 100 parts by weight of the total cleaning product (phep.).

Any chlorine-releasing agent known in 'the art may be satisfactorily utilized in this invention. A chlorinereleasing agent is defined herein as a chlorine-containing compound which liberates chlorine under conditions normally used for cleaning purposes. These agents may range from 0.5 to 40 parts (phep.). Examples of suitable chlorine-releasing agents are as follows. chlorocyanurates, chlorinated trisodium phosphate, Ne'ehlorosuccinimide, calcium hypochlorite, and N,N-dichloroazocarbonamidine.

Soaps and nonsoap detergents, which are usually found in the cleaning products of this invention, are well defined terms of art [Chemistry of Organic Compounds, Noller (1951), pp. 186-90; College Chemistry, Smith (1947), pp. 431-2 and 455]. Any known soap or nonsoap detergent is applicable including the following compounds: sodium lauryl sulfate, sodium alkyldiphenyloxide, alkali metal salts of fatty acids and the wetting agents disclosed in US. Pat. No. 2,263,948 which is incorporated herein by reference. These soaps or detergents may comprise about 0.5 to parts (phep.).

The instant cleaning products generally have an alkali metal phosphate therein. This terminology covers a well known class of compounds employed in cleaning compositions (US. Pat. No. 2,310,475). The orthophosphates, pyrophosphates, polyphosphates and metaphosphates are applicable to the present invention. These phosphates, e.g., sodium tripolyphosphate, may comprise about 1 to 80 parts (phep.).

A soil-suspending agent, e.g., sodium carboxymethylcellulose and polyvinyl alcohol, is advantageously added in certain types of products within the range of about 0.2 to 1.0 parts (phep.). The following ingredients are also frequently employed: other perfume compounds in combination with the dioxane perfumes; abrasives, e.g., silica; metallic strands (for scouring pads); silicates; carbonates; and borates.

The preferred ranges for the various ingredients in different products are indicated in Table I.

TABLE I Preferred range, percent 1 In In In heavy 1n dishwashing dry duty scouring compositions bleach detergents cleansers Soaps or nonsoap detergents:

Sodium lauryl sulfate 1-2 2-4 10-20 2-3 Pluronic L-6l 1 3-4 2-4 8-10 4-5 Pluronic L-62 3 3-4 2-4 8-10 4-5 Sodium alkyldiphenyloxide sulionate 0.6-0.8 2-4 8-10 4-5 Soap 3-4 2-4 40-80 4-5 Soil-suspending agents:

Sod um carboxymethylcellulosenn t 0.3-0.5 Sodium carboxymethyl hydroxy ethyl cellulose 0.3-0. 5 Sodium cellulose sulfate. 0. 3-0. 5 Polyvinyl alcohol 0.3-0. 5 Polyethylene glycols 0.3-0. 5 Chlorine-releasing ag nts.

Trichlorocyanuric acid 8-10 8-10 4-8 8-10 Sodium and potassium dichlorocyanurate 14-16 14-16 5-10 14-16 Divhlorodimethylhydant ion 14-16 14-16 5-10 14-16 N-chlorosuccinimide 14-16 14-16 5-10 14-16 Trichloromelamine 14-16 14-10 5-10 14-16 Calcium hypochlorite 14-16 14-16 4-8 14-16 Chlorinated trisodium phosphate 8-10 8-10 4-8 8-10 Chlorainine-T l 14-16 14-16 5-10 14-16 N,N-dichloro-azocarbonamidine 14-16 14-16 5-10 14-16 Phosphates:

Sodium tripolyphosphate 40-50 5-20 40-50 5-10 Sodium yrophosphate 40-50 5-20 40-50 5-10 Sodium exametaphosphate 40-50 5-20 40-50 5-10 Sodium 'tetraphosphate 40-50 5-20 40-50 5-10 Sodium t-rimetaphosphate (Soluble) 40-50 5-20 40-50 5-10 Abrasives:

Silica 85-95 Volcanic ash 85-95 Diatomaceous earth 85-95 Pumice 85-95 Alumina. 85-95 Feldspar.v 85-95 Carboiundum 85-95 Fine metallic particles 5 Metallic strands L...

Plastic web 5 Other:

Sodium meta-silicate -15 4-8 4-8 RU-sillcate 10-15 4-8 4-8 N-silicate 10-15 4-8 4-8 (l-silicatc 5 10-15 4-8 4-8 Sodium oarbonate.. 5-10 5-10 5-15 Sodium tetraborata. 5-10 5-10 5-15 Sodium scsquicarbonate 5-10 5-10 5-15 Sodium sulfate (to 100%) 1 Percentages are based upon cleaning compound before dioxane perfumes are added ere o.

1 Empirical formula HO(C2II40).(C3HlO)b(C2H|O) CH wherein b is selected to provide a mol. wt. ofpropylene oxide of 1,750 and a-l-c is an integer to provide 10% etnylene oxide in the molecule.

1 Empirical formula HO(C2H4O) '.(ciH.o)i. ciHi0 .u wherein b is selected to provide a mol. wt. of propylene oxide of 1,750 and a-l-c is an integer to provide ethylene oxide in The dioxanes heretofore described ma also be utilized to perfume cleaning compositions without any chlorinerelcasing agents therein. These compositions include liquid detergent formulations, soaps and toiletry products, especially those that are neutral or alkaline. Furthermore, a bleaching-type product may be formed which contains only a dioxane perfume and a chlorine-releasing agent.

Thus, in accordance with this invention, a synthetic perfume with a suitable geranium-rose note has been provided. Furthermore, it is now possible to manufacture a cleaning product comprising a chlorine-releasing agent and a 1,3-dioxanc perfume which can be used without the formation of an objectionable odor.

The following examples are submitted to illustrate but not to limit this invention. Unless otherwise indicated, all parts and percentages in the specification are based on weight.

EXAMPLE 1 The following compounds were mixed in a 250 ml.

flask: 11.4 g. (0.1 mole) of heptaldchyde; 9.9 g. (0.11 mole) of butane-1,3-dio1; 150 ml. of benzene; and 0.25 g. of p-tplucnesulfonic acid. A reaction was performed at a temperature of -85 C. with the water formed therefrom being separated by means of a Dean-Stark trap on the flask. After 3% hours of refluxing, no further water was formed. The reaction mixture was then cooled to room temperature, neutralized with aqueous sodium carbonate and washed with water until neutral.

Subsequent distillation provided 2-hcxyl-4-methyl-1,3- dioxanc which had a geranium-rose note. This dioxane was capable of being used to perfume a dishwasher composition with a chlorine-releasing compound therein.

EXAMPLE 2 The compounds indicated in Table II were prepared in accordance with similar procedures as desc ibed in Example 1.

TABLE II R4\ /B: Rr'C O Compounds R1 R; I R; R4 R5 Rn R1 Rn H H H. H H H H H H H H H H All of the above compounds possessed a geranium-rose note and were suitable for incorporation into a product containing a soap or non-soap detergent and a chlorine releasing agent.

EXAMPLE 3 The compounds listed in Table III were prepared but they did not exhibit a geranium-rose note.

TABLE 111 These bleaches were stored for six days at 95 F. in both closed jars and commercial packages, and the perfume odor was not affected by the chlorine-releasing agents therein.

EXAMPLE 5 A dishwasher product was provided with 0.1% 2-iso- H Isobutyl This example demonstrates the criticality of the substituents on the 1,3 dioxanes in order to provide the desired odoriferous properties.

EXAMPLE 4 Dry chlorinated bleaches were formed with the following ingredients therein.

Parts In edient g A B C 2-isobutyi+methyl-1,3-dioxane 2-n-heptyi-4-methyl-l ,a-dloxane.

2-isobuty1-4,6-dimethyl- Sodium tatty alcohol suitate Potassium dichlorotriazinetrione Sodium tripolyphosphate Sodium silicate Sodium suitate Sodium alkylbenwnesulionnte Helene 1 Primarily a 1:1 mixture 0! aikylbenzene sultonates in which the alkgl, portion is a polypropylene group and has an average of 12 and 15 car n atoms respectively.

I Dichlorodimethylhydantoin.

butyl-4,5,6-trimethyl-l,3-dioxane and the ingredients shown herebelow.

5r Ingredient: Parts Sodium tripolyphosphate 1 44.00

Chlorinated trisodium phosphate 9.60

N-Silicate 1 7.414

RU-Silicate 1 5.878

Pluronic L62 2.25

Pluronic L61 0.75

Colorants 0.004

Water 30.104

1 Expressed on dry basis After storage for six days at 95 F. in both closed jars and commercial packages, this formulation lost none of its perfume odor.

EXAMPLE 6 The following liquid detergent formulation was per- 7 fumed with 0.1% of 2-(2-ethyl-propyl)-4-methyl- 1, 3-0: i-

oxane.

Composition: Percent Potassium dodecylbenzenesulfonate 10 Sodium xylenesulfonate 8 LDA 2 2.7 LIPA 3 3.0 Potassium pyrophosphate 18.0 Sodium silicate 2.5 CMC 4 0.15

Methocel 0.57

Water (to 100% Laurlc myrlstic dlethanol amide. 'Laurlc myrlstlc isopropanol amide. Sodium carboxymethylcellulose.

5 Methylcellulose.

The perfume odor of this formulation was unaffected after being stored in accordance with the procedure described in Example 4.

EXAMPLE 7 The scouring cleanser-type formulation indicated herebelow was perfumed with 0.1% of 2-isobutyl-2,4-dimethyl-1,3-dioxane.

Composition: Parts Silica, 90 mesh 7O Chlorinated trisodium phosphate Sodium alkylbenzene sulfonate 3.33 Sodium tripolyphosphate 16.67

After storage, as per Example 4, the perfume odor was unaffected.

EXAMPLE 8 Two perfumery blends were provided. Blend A contained 20% of 2-isobutyl-4-methyl-1,3-dioxane as the principal source of geranium" odor. Blend B had conventional perfumery materials as the source of geranium character. The blends had the following composition.

C Parts om ition W8 A B Citronellol 200 200 Ciunamle also 500 500 Thyme oil 30 30 Amyl cinnamlc aldehyde. 40

Lin 0o Geranyl acetate 100 The dishwasher product in Example 6 was modified independently with 0.05% of each blend. After storage as described in Example 4, the odor of Blend A remained unchanged. Conversely, the product with Blend B had less geranium odor after storage.

Having set forth the general nature and specific embodiments of the present invention, the true scope is now particularly pointed out in the appended claim.

What is claimed is:

1. A perfume having the structure:

OTHER REFERENCES Mastagli et al.: Compt. Rend., vol. 251 (1960), pp. 2191-3.

NICHOLAS S. RIZZO, Primary Examiner.

J. H. TURNIPSEED, Assistant Examiner.

US. Cl. X.R. 25299, 522 

1. A PERFUME HAVING THE STRUCTURE: 